Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions

ABSTRACT

Compositions including one or more anionic polymerization initiators and one or more additives for improving functionalizing efficiency of living polymer anions are disclosed. The present invention also provides compositions including one or more electrophiles and one or more additives for improving functionalizing efficiency of living polymer anions. Novel electrophiles and processes for improving polymer anion functionalization efficiencies are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 09/897,562; filed Jul. 2, 2001 now U.S. Pat. No. 6,545,103, which isa divisional application of U.S. application Ser. No. 09/301,535 filedApr. 28, 1999, which is a continuation-in-part application of U.S.application Ser. No. 09/189,664, filed Nov. 11, 1998, now abandoned,which is related to Provisional Application Ser. No. 60/065,858, filedNov. 14, 1997, and claim the benefit of its earlier filing date under 35U.S.C. 119(e). The disclosures of each are incorporated by referenceherein in their entireties.

FIELD OF THE INVENTION

This invention relates to novel compositions of an anionicpolymerization initiator and an additive which enhance functionalizationof living polymer anions; novel compositions of electrophiles and anadditive which enhance functionalization of living polymer anions; andprocesses which employ these compositions, or an additive, for improvedefficiency in the functionalization of living polymer anions.

BACKGROUND OF THE INVENTION

Polymers that contain terminal functional groups are industriallyimportant. One technique to prepare these terminally functionalizedpolymers is by reaction of a suitable electrophile with a living polymeranion. For numerous examples of end group functionalization chemistry,see Hsieh, H. L.; Quirk, R. P. Anionic Polymerization: Principles andPractical Applications; Marcel Dekker: New York, N.Y., 1996, pages261-306.

Some of these functionalization reactions are not very efficient,particularly for the preparation of telechelic polymers, due to theformation of a thick gel during the functionalization. This leads tolower capping efficiency. See, for example, U.S. Pat. No. 5,393,843,Example 1, wherein the capping efficiency was only 82%.

A recently reported terminal functionalization technique uses aprotected functionalized electrophile. For instance, Nakahama andco-workers have described the reaction of polystyryllithium with theelectrophile Br—(CH₂)₃C(OCH₃)₃, a protected carboxyl group. See Hirao,A.; Nagahama, H. Ishizone, T.; Nakahama, S. Macromolecules, 1993, 26,2145. Excellent terminal functionalization of the living anion wasachieved (>95%). Other examples of efficient functionalization withprotected functionalized electrophiles are reported in Ueda, K.; Hirao,A.; S. Nakahama, S. Macromolecules, 1990, 23, 939; Tohyama, M.; Hirao,A.; Nakahama, S. Macromol. Chem. Phys. 1996, 197, 3135, and Labeau, M.P.; Cramail, H.; Deffieux, A. Polymer International, 1996, 41, 453.

To obtain efficient functionalization, these functionalization reactionsare conducted in tetrahydrofuran (THF) at −80° C. THF, however, is anexpensive solvent, and these low-temperature conditions are notpractical on an industrial scale. In addition, efficientfunctionalization of polymer anions was only observed with expensivealkyl bromides.

SUMMARY OF THE INVENTION

The present invention provides compositions capable of increasingefficiencies in the functionalization of living polymer anions. Thecompositions include as a component one or more additives, such as analkali halide or alkali alkoxide. The inventors have unexpectedly foundthat the additives are capable of improving the efficiency of reactionsbetween polymer anions and electrophiles, as compared to similarreactions in the absence of an additive. In one aspect of the invention,the compositions include one or more additives and one or more anionicpolymerization initiators. Exemplary anionic polymerization initiatorsinclude non-functionalized and functionalized organoalkali metalinitiators. In another aspect of the invention, the compositions includeone or more additives and one or more electrophiles useful forfunctionalizing living polymers.

Processes for improving living polymer anion functionalization are alsoprovided. In this aspect of the invention, a living polymer anion isfunctionalized using a suitable electrophile in the presence of one ormore additives as described above. Higher yields of functionalizedpolymers were observed when the additive was employed. In addition, theemployment of the additive allowed the functionalization to be performedin hydrocarbon solvent at room temperature. Further, these reactionconditions are much less expensive on a commercial scale, as compared tothe prior art. The invention can also be used with a variety of monomersand/or functionalizing agents. For example, it was discovered that theless expensive, and more readily available, alkyl chlorides affordefficient functionalization when an additive is employed.

Yet another embodiment of the invention provides novel electrophiles.The novel electrophiles have the formula

wherein:

X is halogen selected from chloride, bromide and iodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, nitrogen, andmixtures thereof;

(A-R₁R₂R₃) is a protecting group, in which A is an element selected fromGroup IVa of the Periodic Table of the Elements and R₁, R₂, and R₃ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

R, R₄, and R₅ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen; and

l is an integer from 1 to 7.

DETAILED DESCRIPTION OF THE INVENTION

Additives useful in the invention include, but are not limited to,alkali halides, such as lithium chloride, lithium bromide, lithiumiodide, sodium chloride, sodium iodide, potassium chloride, and mixturesthereof; alkali alkoxides, such as lithium t-butoxide, lithiums-butoxide, potassium t-butoxide, and mixtures thereof; and the like andmixtures thereof. The additives should be dried, prior to use.

Several factors influence the amount of additive required, such as thenature of the polymer anion; the identity of the hydrocarbon solvent;the presence of a polar additive (co-solvent); the amount of the polaradditive; the nature of the electrophile; and the identity of theadditive. An effective amount of the additive employed is from as littleas 0.01 equivalents of the electrophile, up to greater than fiveequivalents again based on the electrophile. In general, less than tenequivalents of the additive are effective for increasing the efficiencyof the functionalization reaction.

In one aspect of the invention, the compositions can include one or moreorganoalkali metal anionic polymerization initiators. Exemplary anionicpolymerization initiators include alkyllithium initiatiors representedby the formula R′—Li, wherein R′ represents an aliphatic,cycloaliphatic, or arylsubstituted aliphatic radical. Preferably, R′ isan alkyl or substituted alkyl group of 1-12 carbon atoms. Suchinitiators include, but are not limited to, methyllithium, ethyllithium,n-propyllithium, 2-propyllithium, n-butyllithium, s-butyllithium,t-butyllithium, n-hexyllithium, 2-ethylhexyllithium, and the like andmixtures thereof. As used herein, alkyllithium initiators also includedilithium initiators as known in the art. See, for example, U.S. Pat.Nos. 5,393,843 and 5,405,911. Dilithium initiators can be prepared bythe reaction of an alkyllithium reagent, such as s-butyllithium, with acompound having at least two independently polymerizable vinyl groups,such as the isomeric divinylbenzenes or isomeric diisopropenylbenzenes.

One or more functionalized organoalkali metal initiators may also beemployed in the compositions of the invention. These functionalizedinitiators have the general structure shown below:

wherein:

M is an alkali metal selected from the group consisting of lithium,sodium and potassium;

Q is an unsaturated hydrocarbyl group derived by incorporation of one ormore conjugated diene hydrocarbons, one or more alkenylsubstitutedaromatic compounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds into the M-Z linkage;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A-R₇R₈R₉)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements, and R₇, R₈, and R₉are each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

l is an integer from 1 to 7; and

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.

As used herein, the term “alkyl” refers to straight chain and branchedC1-C25 alkyl. The term “substituted alkyl” refers to C1-C25 alkylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. The term “cycloalkyl” refers to C3-C12cycloalkyl. The term “substituted cycloalkyl” refers to C3-C12cycloalkyl substituted with one or more lower C1-C10 alkyl, loweralkoxy, lower alkylthio, or lower dialkylamino. The term “aryl” refersto C5-C25 aryl having one or more aromatic rings, each of 5 or 6 carbonatoms. Multiple aryl rings may be fused, as in naphthyl or unfused, asin biphenyl. The term “substituted aryl” refers to C5-C25 arylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. Exemplary aryl and substituted arylgroups include, for example, phenyl, benzyl, and the like.

U.S. Pat. Nos. 5,496,940 and 5,527,753 disclose novel, tertiary aminoinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-tertiary-amino-1-haloalkanes of the following general structures:

wherein X is defined as a halogen, preferably chlorine or bromine; Z isdefined as a branched or straight chain hydrocarbon connecting groupwhich contains 3-25 carbon atoms; A is an element selected from GroupIVa of the Periodic Table of the Elements, R¹, R² and R³ areindependently defined as hydrogen, alkyl, substituted alkyl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,aryl or substituted aryl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, or cycloalkyl and substituted cycloalkylgroups containing 5 to 12 carbon atoms, and m is an integer from 1 to 7.The process reacts selected omega-tertiary-amino-1-haloalkanes whosealkyl groups contain 3 to 25 carbon atoms, with lithium metal at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane, or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

Tertiary amino-1-haloalkanes useful in the practice of this inventioninclude, but are not limited to, 3-(N,N-dimethylamino)-1-propyl halide,3-(N,N-dimethylamino)-2-methyl-1-propyl halide,3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-dimethylamino)-1-butyl halide, 5-(N,N-dimethylamino)-1-pentylhalide, 6-(N,N-dimethylamino)-1-hexyl halide,3-(N,N-diethylamino)-1-propyl halide,3-(N,N-diethylamino)-2-methyl-1-propyl halide,3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentylhalide, 6-(N,N-diethylamino)-1-hexyl halide,3-(N-ethyl-N-methylamino)-1-propyl halide,3-(N-ethyl-N-methylamino)-2-methyl-1 -propyl halide,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide,4-(N-ethyl-N-methylamino)-1-butyl halide,5-(N-ethyl-N-methylamino)-1-pentyl halide,6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propylhalide, 3-(piperidino)-2-methyl-1-propyl halide,3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butylhalide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl halide,3-(pyrrolidino)-1-propyl halide, 3-(pyrrolidino)-2-methyl-1-propylhalide, 3-(pyrrolidino)-2,2-dimethyl-1-propyl halide,4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide,6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl halide,3-(hexamethyleneimino)-2-methyl-1-propyl halide,3-(hexamethyleneimino)-2,2-dimethyl-1-propyl halide,4-(hexamethyleneimino)-1-butyl halide, 5-(hexamethyleneimino)-1-pentylhalide, 6-(hexamethyleneimino)-1-hexyl halide,3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-propyl halide,4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-butyl halide,6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-hexyl halide,3-(N-isopropyl-N-methyl)-1-propyl halide,2-(N-isopropyl-N-methyl)-2-methyl-1-propyl halide,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide group isselected from chlorine and bromine.

U.S. Pat. No. 5,600,021 discloses novel monofunctional ether initiatorswhich are soluble in hydrocarbon solvents. These initiators, useful inpracticing this invention, are derived fromomega-protected-hydroxy-1-haloalkanes of the following generalstructure:X—Z—O—(C—R¹R²R³)wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms, R¹, R² and R³ are independently defined as hydrogen,alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, aryl or substituted aryl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,or cycloalkyl and substituted cycloalkyl groups containing 5 to 12carbon atoms. The process reacts selectedomega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25carbon atoms, with lithium metal at a temperature between about 35° C.and about 130° C., preferably at the reflux temperature of an alkane,cycloalkane, or aromatic reaction solvent containing 5 to 10 carbonatoms and mixtures of such solvents.

The precursor omega-protected-1-haloalkanes (halides) were prepared fromthe corresponding haloalcohol by the standard literature methods. Forexample, 3-(1,1-dimethylethoxy)-1-chloropropane was synthesized by thereaction of 3-chloro-1-propanol with 2-methylpropene according to themethod of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters,29, 1988, 2951. The method of B. Figadere, X. Franck and A. Cave,Tetrahedron Letters, 34, 1993, 5893, which involved the reaction of theappropriate alcohol with 2-methyl-2-butene catalyzed by borontrifluoride etherate is employed for the preparation of the t-amylethers. The alkoxy, alkylthio or dialkylamino substituted ethers, forexample 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, were synthesizedby reaction of the corresponding substituted alcohol, for instance3-methylthio-1-propanol, with an alpha-bromo-omega-chloroalkane, forinstance 1-bromo-6-hexane, according to the method of J. Almena, F.Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883. The compound4-(methoxy)-1-chlorobutane, and the higher analogs, were synthesized bythe ring opening reaction of tetrahydrofuran with thionyl chloride andmethanol, according to the procedure of T. Ferrari and P. Vogel,SYNLETT, 1991, 233. The triphenylmethyl protected compounds, for example3-(triphenylmethoxy)-1-chloropropane, are prepared by the reaction ofthe haloalcohol with triphenylmethylchloride, according to the method ofS. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.

Omega-hydroxy-protected-1-haloalkanes prepared in accord with thisearlier process useful in practicing this invention can include, but arenot limited to, 3-(1,1-dimethylethoxy)-1-propyl halide,3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide,3-((1,1-dimethylethoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylethoxy)-1-butyl halide, 5-(1,1-dimethylethoxy)-1-pentylhalide, 6-(1,1-dimethylethoxy)-1-hexyl halide,8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1-propylhalide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylpropoxy)-1-butyl halide, 5-(1,1-dimethylpropoxy)-1-pentylhalide, 6-(1,1-dimethylpropoxy)-1-hexyl halide,8-(1,1-dimethylpropoxy)-1-octyl halide, 4-(methoxy)-1-butyl halide,4-(ethoxy)-1-butyl halide, 4-(propyloxy)-1-butyl halide,4-(1-methylethoxy)-1-butyl halide,3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide,4-(triphenylmethoxy)-1-butyl halide,3-[3-(dimethylamino)-1-propyloxy]-1-propyl halide, 3-[2-(dimethylamino)1-ethoxy]-1-propyl halide, 3-[2-(diethylamino)-1-ethoxy]-1-propylhalide, 3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyl halide,3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl halide,4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide,6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide,3-[2-(methoxy)-1-ethoxy]-1-propyl halide,3-[2-(ethoxy)-1-ethoxy]-1-propyl halide,4-[2-(methoxy)-1-ethoxy]-1-butyl halide,5-[2-(ethoxy)-1-ethoxy]-1-pentyl halide,3-[3-(methylthio)-1-propyloxy]-1-propyl halide,3-[4-(methylthio)-1-butyloxy]-1-propyl halide,3-(methylthiomethoxy)-1-propyl halide,6-[3-(methylthio)-1-propyloxy]-1-hexyl halide,3-[4-(methoxy)-benzyloxy]-1-propyl halide,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyl halide,3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide,8-[4-(methoxy)-benzyloxy]-1-octyl halide,4-[4-(methylthio)-benzyloxy]-1-butyl halide,3-[4-(dimethylamino)-benzyloxy]-1-propyl halide,6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide,5-(triphenylmethoxy)-1-pentyl halide, 6-(triphenylmethoxy)-1-hexylhalide, and 8-(triphenylmethoxy)-1-octyl halide. The halo- or halidegroup is selected from chlorine and bromine.

U.S. Pat. No. 5,362,699 discloses novel monofunctional silyl etherinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-silyl-protected-hydroxy-1-haloalkanes of the following generalstructure:X—Z—O—(Si—R¹R²R³)wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms, optionally containing aryl or substituted aryl groups; andR¹, R², and R³ are independently defined as saturated and unsaturatedaliphatic and aromatic radicals, and their employment as initiators inthe anionic polymerization of olefin containing monomers in an inert,hydrocarbon solvent optionally containing a Lewis base. The processreacts selected omega-hydroxy-protected-1-haloalkanes whose alkyl groupscontain 3 to 25 carbon atoms, with lithium metal at a temperaturebetween about 25° C. and about 40° C., in an alkane, cycloalkane oraromatic reaction solvent containing 5 to 10 carbon atoms and mixturesof such solvents.

t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilyloxy)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding halo-alcohol,according to the method described in U.S. Pat. No. 5,493,044.Omega-silyloxy-1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention can include, but are notlimited to, 3-(t-butyldimethylsilyloxy)-1-propyl halide,3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide,4-(t-butyldimethylsilyloxy)-1-butyl halide,5-(t-butyldimethyl-silyloxy)-1-pentyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide,8-(t-butyldimethylsilyloxy)-1-octyl halide,3-(t-butyldiphenylylsilyloxy)-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide, and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or halidegroup is selected from chlorine and bromine.

Monofunctional thioether initiators useful in the practice of thisinvention are derived from omega-protected-thio-1-haloalkanes of thefollowing general structure:X—Z—S—(A-R¹R²R³)wherein X is defined as a halogen, preferably chlorine or bromine; Z isa branched or straight chain hydrocarbon group which contains 3-25carbon atoms; (A-R¹R²R³) is a protecting group in which A is an elementselected from Group IVa of the Periodic Table of the Elements; R¹, R²,and R³ are independently defined as hydrogen, alkyl, substituted alkylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, aryl or substituted aryl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, or cycloalkyl and substitutedcycloalkyl groups containing 5 to 12 carbon atoms. The process reactsselected omega-thioprotected-1-haloalkyls whose alkyl groups contain 3to 25 carbon atoms, with lithium metal at a temperature between about35° C. and about 130° C., preferably at the reflux temperature of analkane, cycloalkane or aromatic reaction solvent containing 5 to 10carbon atoms and mixtures of such solvents.

The initiator precursor, omega-thio-protected-1-haloalkanes (halides),are prepared from the corresponding halothiol by the standard literaturemethods. For example, 3-(1,1-dimethylethylthio)-1-propylchloride issynthesized by the reaction of 3-chloro-1-propanthiol with2-methylpropene according to the method of A. Alexakis, M. Gardette, andS. Colin, Tetrahedron Letters, 29, 1988, 2951. Alternatively, reactionof 1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a baseaffords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of B.Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893,which involved the reaction of the appropriate thiol with2-methyl-2-butene catalyzed by boron trifluoride etherate is employedfor the preparation of the t-amyl thioethers. Additionally,5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by themethod of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995,11883. This synthesis involves the reaction of the appropriate thiolwith an alkyllithium, then reaction of the lithium salt with thecorresponding alpha, omega dihalide. 3-(Methylthio)-1-propylchloride canbe prepared by chlorination of the corresponding alcohol with thionylchloride, as taught by D. F. Taber and Y. Wang, J. Org, Chem., 58, 1993,6470. Methoxymethylthio compounds, such as6-(methoxymethylthio)-1-hexylchloride, are prepared by the reaction ofthe omega-chloro-thiol with bromochloromethane, methanol, and potassiumhydroxide, by the method of F. D. Toste and I. W. J. Still, Synlett,1995, 159. t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilylthio)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding thiol, according tothe method described in U.S. Pat. No. 5,493,044.

Omega-thio-protected 1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention can include, but are notlimited to, 3-(methylthio)-1-propylhalide,3-(methylthio)-2-methyl-1-propylhalide,3-(methylthio)-2,2-dimethyl-1-propylhalide,4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide,6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide,3-(methoxymethylthio) 1-propylhalide,3-(methoxymethylthio)-2-methyl-1-propylhalide,3-(methoxymethylthio)-2,2-dimethyl-1-propylhalide,4-(methoxymethylthio)-1-butylhalide,5-(methoxymethylthio)-1-pentylhalide,6-(methoxymethylthio)-1-hexylhalide,8-(methoxymethylthio)-1-octylhalide,3-(1,1-dimethylethylthio)-1-propylhalide,3-(1,1-dimethylethylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylethylthio)-1-butylhalide,5-(1,1-dimethylethylthio)-1-pentylhalide,6-(1,1-dimethylethylthio)-1-hexylhalide,8-(1,1-dimethylethylthio)-1-octylhalide,3-(1,1-dimethylpropylthio)-1-propylhalide,3-(1,1-dimethylpropylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylpropylthio)-1-butylhalide,5-(1,1-dimethylpropylthio)-1-pentylhalide,6-(1,1-dimethylpropylthio)-1-hexylhalide,8-(1,1-dimethylpropylthio)-1-octylhalide,3-(cyclopentylthio)-1-propylhalide,3-(cyclopentylthio)-2-methyl-1-propylhalide,3-(cyclopentylthio)-2,2-dimethyl-1-propylhalide,4-(cyclopentylthio)-1-butylhalide, 5-(cyclopentylthio)-1-pentylhalide,6-(cyclopentylthio)-1-hexylhalide, 8-(cyclopentylthio)-1-octylhalide,3-(cyclohexylthio)-1-propylhalide,3-(cyclohexylthio)-2-methyl-1-propylhalide,3-(cyclohexylthio)-2,2-dimethyl-1-propylhalide,4-(cyclohexylthio)-1-butylhalide, 5-(cyclohexylthio)-1-pentylhalide,6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide,3-(t-butyldimethylsilylthio)-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,4-(t-butyldimethylsilylthio)-1-butylhalide,6-(t-butyldimethylsilylthio)-1-hexylhalide and3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or halidegroup is selected from chlorine and bromine.

Functionalized organoalkali metal initiators of the following structuresmay also be employed in the compositions of the invention:

wherein:

M is an alkali metal;

R¹⁰ is chiral or achiral and is selected from the group consisting ofsaturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C3-C16 alkyl; and saturated and unsaturated,linear and branched, C3-C16 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl;

R¹¹ is chiral or achiral and is selected from the group consisting ofsaturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C1-C16 alkyl; saturated and unsaturated,optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;saturated and unsaturated, linear and branched, substituted C1-C16 alkylcontaining saturated or unsaturated lower alkyl, aryl, or substitutedaryl; and saturated and unsaturated substituted C3-C16 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substitutedaryl;

R¹² is a hydrocarbon connecting group or tether selected from the groupconsisting of saturated and unsaturated, linear and branched C1-C25alkyl; saturated and unsaturated C3-C25 cycloalkyl; saturated andunsaturated substituted C1-C25 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl; and saturated and unsaturatedsubstituted C3-C25 cycloalkyl containing saturated or unsaturated loweralkyl, aryl, or substituted aryl, with the proviso that the nitrogenatom and the alkali metal are separated by three or more carbon atoms;

Q is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds into the M-R¹²linkage; and

n is an integer from 1 to 5. See pending U.S. application Ser. No.09/139,222, filed Aug. 24, 1998, the entire disclosure of which ishereby incorporated by reference.

The tertiary amino initiators of this invention are prepared by reactionof selected tertiary amino halides, such as described in FIG. 4, with analkali metal selected from lithium, sodium and potassium, for example ata temperature ranging from about 35 to 130° C., advantageously at anelevated temperature (>40° C.), in a hydrocarbon solvent containing fiveto ten carbon atoms and mixtures of such solvents to form analkylorganometallic compound containing a tertiary amine.

wherein:

X is halogen selected from the group consisting of chlorine, bromine andiodine; and R¹⁰, R¹¹, and R¹² are as defined above. These halides arecommercially available or can be prepared using techniques known in theart.

Examples of tertiary amino halides useful in the practicing thisinvention include, but are not limited to,2-(2-chloroethyl)-N-methylpiperidine,2-(2-chloroethyl)-N-ethylpiperidine,2-(2-chloroethyl)-N-propylpiperidine,2-(2-chloroethyl)-N-methylpyrrolidine,2-(2-chloroethyl)-N-ethylpyrrolidine,3-(chloromethyl)-N-methylpiperidine, 3-(chloromethyl)-N-ethylpiperidine,4-(2-chloroethyl)-N-methylpiperidine,4-(2-chloroethyl)-N-ethylpiperidine,4-(2-chloroethyl)-N-propylpiperidine,4-(chloromethyl)-N-methylpiperidine, 4-(chloromethyl)-N-ethylpiperidine,4-(chloromethyl)-N-propylpiperidine,2-(2-chloroethyl)-N-methylhexamethyleneimine,2-(2-chloroethyl)-N-methylmorpholine, and mixtures thereof.

The chain extended compounds of FIG. 5 can have greater solubility inhydrocarbon solution than the compounds described in FIG. 3. Forexample, the solubility of 2-(2-lithioethyl)-N-methyl-piperidine incyclohexane solution was about 6 weight percent. However, when this samematerial was chain extended with two equivalents of isoprene, thesolubility increased to over 28 weight percent. Similar increases insolubility were observed for other chain extended analogues.

The initiators described in FIG. 5 are prepared by reacting anorganometallic compound of the formula described in FIG. 3 wherein M,R¹⁰, R¹¹, and R¹² have the meanings ascribed above, with one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromaticcompounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds, to form an extended hydrocarbonchain between M and R¹² in FIG. 5, which extended chain is denoted asQ_(n) in FIG. 5. The compounds of FIG. 5 are prepared by first reactingin an inert solvent a selected tertiary amino halide (FIG. 4) with analkali metal at a temperature ranging from about 35° C. to about 130°C., advantageously at a temperature above about 40° C., to afford anorganometallic compound of FIG. 3, which is then optionally reacted witha one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds, in apredominantly alkane, cycloalkane, or aromatic reaction solvent, whichsolvent contains 5 to 10 carbon atoms, and mixtures of such solvents toproduce an initiator with an extended chain or tether between the metalatom (M) and R¹² in FIG. 5 above and mixtures thereof with compounds ofFIG. 3.

Incorporation of Q groups into the M-R¹² linkage to form the compoundsof FIG. 5 above involves addition of compounds of FIG. 3 across thecarbon to carbon double bonds in compounds selected from the consistingof one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds to produce newcarbon-lithium bonds of an allylic or benzylic nature, similar to thosefound in a propagating polyalkadiene or polyarylethylene polymer chainderived by anionic initiation of the polymerization of conjugated dienesor arylethylenes. These new carbonBlithium bonds are now “activated”toward polymerization and so are much more efficient in promotingpolymerization than the precursor M-R¹² (M=Li) bonds themselves.

In another aspect of the invention, the compositions include one or moreadditives and one or more electrophiles. The electrophiles can, forexample, include one or more functionalized alkyl halides(electrophiles). Co-pending U.S. patent application Ser. Nos.08/872,895, 08/873,220, and 08/893,951, incorporated herein byreference, detail the synthesis of telechelic and functionalized starpolymers by the reaction of living polymer anions with electrophiles ofthe following general structure:

wherein:

X is halogen selected from the group consisting of chloride, bromide andiodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally containing aryl or substitutedaryl groups;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A-R⁷R⁸R⁹)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements, and R⁷, R⁸, and R⁹are each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

l is an integer from 1 to 7.

Examples of electrophiles of this class include, but are not limited to,3-(N,N-dimethylamino)-1-chloropropane,3-(N,N-dimethylamino)-1-bromopropane,3-(N,N-dimethylamino)-2-methyl-1-chloropropane,3-(N,N-dimethylamino)-2,2-dimethyl-1-chloropropane,4-(N,N-dimethylamino)-1-chlorobutane,5-(N,N-dimethylamino)-1-chloropentane,3-(N,N-diethylamino)-2-methyl-1-chloropropane,3-(N-ethyl-N-methylamino)-1-chloropropane,6-(N,N-dimethylamino)-1-chlorohexane,3-(N,N-diethylamino)-1-chloropropane,3-(N,N-diethylamino)-2,2-dimethyl-1-chloropropane,4-(N,N-diethylamino)-1-chlorobutane,5-(N,N-diethylamino)-1-chloropentane,6-(N,N-diethylamino)-1-chlorohexane,3-(N-ethyl-N-methylamino)-2-methyl-1-chloropropane,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-chloropropane,4-(N-ethyl-N-methylamino)-1-chlorobutane,5-(N-ethyl-N-methylamino)-1-chloropentane,6-(N-ethyl-N-methylamino)-1-chlorohexane,3-(piperidino)-1-chloropropane, 3-(piperidino)-2-methyl-1-chloropropane,3-(piperidino)-2,2-dimethyl-1-chloropropane,4-(piperidino)-1-chlorobutane, 5-(piperidino)-1-chloropentane,6-(piperidino)-1-chlorohexane, 3-(pyrrolidino)-1-chloropropane,3-(pyrrolidino)-2-methyl-1-chloropropane,3-(pyrrolidino)-2,2-dimethyl-1-chloropropane,4-(pyrrolidino)-1-chlorobutane, 5-(pyrrolidino)-1-chloropentane,6-(pyrrolidino)-1-chlorohexane, 3-(hexamethyleneimino)-1-chloropropane,3-(hexamethyleneimino)-2-methyl-1-chloropropane,3-(hexamethyleneimino)-2,2-dimethyl-1-chloropropane,4-(hexamethyleneimino)-1-chlorobutane,5-(hexamethyleneimino)-1-chloropentane,6-(hexamethyleneimino)-1-chlorohexane,3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chloropropane,4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorobutane,6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-chlorohexane,3-(N-isopropyl-N-methyl)-1-chloropropane,2-(N-isopropyl-N-methyl)-2-methyl-1-chloropropane,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-chloropropane,4-(N-isopropyl-N-methyl)-1-chlorobutane,3-(1,1-dimethylethoxy)-1-chloropropane,3-(1,1-dimethylethoxy)-1-bromopropane,3-(1,1-dimethylethoxy)-2-methyl-1-chloropropane,3-(1,1-dimethylethoxy)-2,2-dimethyl 1-chloropropane,4-(1,1-dimethylethoxy)-1-chlorobutane,5-(1,1-dimethylethoxy)-1-chloropentane,6-(1,1-dimethylethoxy)-1-chlorohexane,8-(1,1-dimethylethoxy)-1-chlorooctane,3-(1,1-dimethylpropoxy)-1-chloropropane,3-(1,1-dimethylpropoxy)-2-methyl-1-chloropropane,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-chloropropane,3-(t-butyldimethylsilyloxy)-1-chloropropane,3-(t-butyldimethyl-silyloxy)-2-methyl-1-chloropropane,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-chloropropane,4-(t-butyldimethylsilyloxy)-1-chlorobutane,4-(t-butyldimethylsilyloxy)-1-iodobutane,5-(t-butyldimethyl-silyloxy)-1-chloropentane,6-(t-butyldimethylsilyloxy)-1-chlorohexane,8-(t-butyldimethylsilyloxy)-1-chlorooctane,3-(t-butyldiphenylylsilyloxy)-1-chloropropane,3-(t-butyldiphenylylsilyloxy)-2-methyl-1-chloropropane,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-chloropropane,6-(t-butyldimethylsilyloxy)-1-chlorohexane,3-(trimethylsilyloxy)-2,2-dimethyl-1-chloropropane,3-(trimethylsilyloxy)-2,2-dimethyl-1-bromopropane and3-(trimethylsilyloxy)-2,2-dimethyl-1-chloropropane,3-(methylthio)-1-chloropropane, 3-(methylthio)-1-bromopropane,3-(methylthio)-2-methyl-1-chloropropane,3-(methylthio)-2,2-dimethyl-1-chloropropane,4-(methylthio)-1-chlorobutane, 5-(methylthio)-1-chloropentane,6-(methylthio)-1-chlorohexane, 8-(methylthio)-1-chlorooctane,3-(methoxymethylthio)-1-chloropropane,3-(methoxymethylthio)-2-methyl-1-chloropropane,3-(methoxymethylthio)-2,2-dimethyl 1-chloropropane,4-(methoxymethylthio)-1-chlorobutane,5-(methoxymethylthio)-1-chloropentane,3-(1,1-dimethylpropylthio)-1-chloropropane,3-(1,1-dimethylpropylthio)-2-methyl-1-chloropropane, and3-(t-butyldimethylsilylthio)-1-chloropropane.

Functionalizing agents, or electrophiles, of the formulaX-Z-T-(A-R⁷R⁸R⁹)_(m) or

can be prepared as described, for example, in International PublicationWO 97/16465. In addition, the electrophiles can be prepared as describedin K. Ueda, A. Hirao, and S. Nakahama, Macromolecules, 23, 939 (1990);U.S. Pat. No. 5,496,940; U.S. Pat. No. 5,600,021; U.S. Pat. No.5,362,699; A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters,29, 1988, 2951; B. Figadere, X. Franck, and A. Cave, TetrahedronLetters, 34, 1993, 5893; J. Almena, F. Foubelo, and M. Yus, Tetrahedron,51, 1995, 11883; D. F. Taber and Y. Wang, J. Org. Chem., 58, 1993, 6470;F. D. Toste and I. W. J. Still, Synlett, 1995, 159; and U.S. Pat. No.5,493,044.

Additional electrophiles that are useful in the practice of thisinvention include:

wherein:

X is a halogen selected from chloride, bromide and iodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, nitrogen, andmixtures thereof;

(A-R₁R₂R₃) is a protecting group, in which A is an element selected fromGroup IVa of the Periodic Table of the Elements and R₁, R₂, and R₃ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl;

R, R₄, and R₅ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen;

l is an integer from 1 to 7;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

n is 2 or 3.

Examples of electrophiles of this class include, but are not limited to,trimethyl 4-bromoorthobutyrate, trimethyl 3-chloroorthopropionate,5-chloro-2-pentanone ethylene ketal, triethyl 5-chloroorthopentanoate,N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane, and thelike and mixtures thereof.

These electrophiles can be prepared by standard literature procedures.For example, triethyl ortho-3-chloropropionate can be prepared from3-chloroprionitrile by the method of G. Casy, J. W. Patterson, and R. J.K. Taylor, Org. Syn. Coll. Vol. 8, 415 (1993). Substituted dimethyl ordiethyl dithio acetals and ketals can be prepared from the correspondinghalo aldehydes or halo ketones and methylthiol or ethylthiol and HClcatalyst, as described by H. Zinner, Chem. Ber., 83, 275 (1980). Halosubstituted 1,3-dithianes can be synthesized from the corresponding halocarbonyl compound, 1,3-propanedithiol, and boron trifluoride etheratecatalyst, as detailed by J. A. Marshall and J. L. Belletire, TetrahedronLetters, 871 (1971). Analogously, halo substituted 1,3-dithiolanes canbe synthesized from the corresponding halo carbonyl compound,1,3-ethanedithiol, and boron trifluoride etherate catalyst, as detailedby R. P. Hatch, J. Shringarpure, and S. M. Weinreb, J. Org. Chem., 43,4172 (1978). Substituted dimethyl or diethyl acetals and ketals can beprepared from the corresponding halo aldehydes or halo ketones andmethanol or ethanol and anhydrous HCl catalyst, as described by A. F. B.Cameron, J. S. Hunt, J. F. Oughton, P. A. Wilkinson, and B. M. Wilson,J. Chem. Soc., 3864 (1953). The method of R. A. Daignault and E. L.Eliel, Org. Syn. Col. Vol. V, 303, (1973), which involves the reactionof a halo-substituted aldehyde or ketone with ethylene glycol, withparatolunesulfonic acid catalyst and azeotropic removal of water, can beemployed to prepare the corresponding halo-substituted 1,3-dioxolane.Halo-substituted 1,3-dioxanes can be prepared from the correspondinghalo aldehyde or ketone, 1,3-propanediol, paratoluenesulfonic acidcatalyst, with azeotropic removal of water, see J. E. Cole, W. S.Johnson, P. A. Robins, and J. Walker, J. Chem. Soc., 244 (1962), and H.Okawara, H. Nakai, and M. Ohno, Tetrahedron Letters, 23, 1087 (1982).The reaction of 2-mercaptoethanol with a halo-substituted aldehyde orketone, with zinc chloride catalyst affords the commensurate substituted1,3-oxathiolane, as reported by J. Romo, G. Rosenkranz, and C. Djerassi,J. Amer. Chem. Soc., 73, 4961 (1951) and V. K. Yadav and A. G. Fallis,Tetrahedron Letters, 29, 897 (1988). Substituted oxazolidines can besynthesized from the corresponding aminoalcohol and a halo-substitutedaldehyde or ketone, see E. P. Goldberg and H. R. Nace, J. Amer. Chem.Soc., 77, 359 (1955). In a similar fashion, the method of A. J.Carpenter and D. J. Chadwick, Tetrahedron, 41, 3803 (1985) can beemployed to generate N,N′-dimethylimidazolidines from a halo aldehyde orketone and N,N′-dimethyl-1,2-ethylenediamine. Higher homologs can beprepared from the parent halo-substituted imidazolidine viadialkylation, see J. C. Craig and R. J. Young, Org. Syn. Coll. Vol. V,88 (1973). N-3-Chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentanecan be prepared by the reaction of 3-chloropropylamine and1,1,4,4-tetramethyl-1,4-dichlorodisilethylene and an acid acceptor, seeS. Djuric, J. Venit, and P. Magnus, Tetrahedron Letters, 22, 1787(1981).

An additional class of electrophile that is useful in the practice ofthis invention is described by the general formula:X-Z-Si—[T-(A-R₁R₂R₃)_(m)]_(n)  (VI)wherein:

X is halogen selected from the group consisting of chloride, bromide andiodide;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

A is an element selected from Group IVa of the Periodic Table of theElements;

R₁, R₂, and R₃ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl;

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

n is 2 or 3.

Examples of electrophiles of this class include, but are not limited to,3-chloropropyltrimethoxysilane, chloromethyltriethoxysilane,4-chlorobutyltrimethoxysilane, 3-chloropropyl-tris(dimethylamino)silane,and the like and mixtures thereof.

An additional class of electrophile that is useful in the practice ofthis invention is described by the general formula:

wherein:

Z′ is a halogen atom;

R₁₃ is selected from the group consisting of organic groups containingfrom 1 to about 12 carbon atoms and a bridging bond;

each R₁₄ is independently selected from the group consisting ofhydrogen, organic groups containing from 1 to about 12 carbon atoms anda bridging bond;

each R₁₅ is independently selected from the group consisting ofhydrogen, organic groups containing from 1 to about 12 carbon atoms;

a is an integer from 4 to about 16; and

b is an integer from 0 to about 12.

See U.S. Pat. No. 5,736,617.

Other compounds useful in functionalizing polymeric living polymersinclude, but are not limited to, alkylene oxides, such as ethyleneoxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur;carbon dioxide; halogens such as chlorine, bromine and iodine; propargylhalides; alkenylhalosilanes and omega-alkenylarylhalosilanes, such asstyrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propanesultone; amides, including cyclic amides, such as caprolactam,N-benzylidene trimethylsilylamide, and dimethyl formamide; siliconacetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allylbromide and allyl chloride; methacryloyl chloride; amines, includingprimary, secondary, tertiary and cyclic amines, such as3-(dimethylamino)-propyl chloride andN-(benzylidene)trimethylsilylamine; epihalohydrins, such asepichlorohydrin, epibromohydrin, and epiiodohydrin, and other materialsas known in the art to be useful for terminating or end cappingpolymers. These and other useful functionalizing agents are described,for example, in U.S. Pat. Nos. 3,786,116 and 4,409,357, the entiredisclosure of each of which is incorporated herein by reference.

The impact of the additive was initially studied in thefunctionalization reaction of poly(styryl)lithium. The living polymeranion was treated with 1.5 molar equivalents of3-(N,N-dimethylamino)-1-chloropropane (Examples 1 and 2). The degree offunctionalization was determined by end group titration. The results,tabulated below, indicate that the efficiency of the functionalizationreaction increased by approximately 40% by the addition of 1.5equivalents of dry lithium chloride. Similar results were observed forthe functionalization of poly(isoprenyl) lithium (Examples 3 and 4). Thefunctionalization efficiency increased by greater than 25% when theadditive, lithium chloride, was employed.

Example Sample M_(n) MWD Additive Function 1 PS-Nme₂ 4.0 × 10³ 1.07 LiCl0.92 2 PS-Nme₂ 2.2 × 10³ 1.05 None 0.65 3 PI-Nme₂ 3.9 × 10³ 1.08 LiCl1.02 4 PI-Nme₂ 1.8 × 10³ 1.08 None 0.81

This invention also provides processes for preparing functionalizedpolymers. In the processes of the invention, an additive as describedabove is used to improve the functionalization of polymer anions withelectrophiles, including alkyl halide electrophiles. The processes forthe anionic polymerization of anionically polymerizable monomerscomprise initiating polymerization of a conjugated diene hydrocarbonmonomer, a mixture of conjugated diene monomers, an alkenylsubstitutedaromatic compound, a mixture of alkenylsubstituted aromatic compounds,or a mixture of one or more conjugated diene hydrocarbons and one ormore alkenylsubstituted aromatic compounds in a hydrocarbon or mixedhydrocarbon-polar solvent medium at a temperature of 10° C. to 150° C.with one or more initiators having the formula:

wherein M, Q, Z, A, R′, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², l, m, and n are asdefined above to produce an intermediate living polymer. The monomerscan be polymerized singly, sequentially or as a mixture thereof.

The intermediate living polymer is then reacted with one or moreelectrophiles, such as those described above, in the presence of anadditive, also as described above. The resultant linear or branchedmonofunctional, homotelechelic, heterotelechelic, polymer having one ormore terminal functional groups can be recovered.

The additive, or mixture of additives, can be added to the reactor atthe beginning of the polymerization, as a component of the initiatorcomposition, during the polymerization, after the polymerization butprior to the functionalization, or as a component of thefunctionalization formulation.

Monomer(s) to be anionically polymerized to form living polymer anionscan be selected from any suitable monomer capable of anionicpolymerization, including conjugated alkadienes, alkenylsubstitutedaromatic hydrocarbons, and mixtures thereof. Examples of suitableconjugated alkadienes include, but are not limited to, 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.

Examples of polymerizable alkenylsubstituted aromatic hydrocarbonsinclude, but are not limited to, styrene, alpha-methylstyrene,vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene andmixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl andarylalkyl derivatives thereof in which the total number of carbon atomsin the combined hydrocarbon constituents is generally not greater than18. Examples of these latter compounds include 3-methylstyrene,3,5-diethylstyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene and4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404, incorporatedherein by reference in its entirety, discloses suitable additionalalkenylsubstituted aromatic compounds.

The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerization in the presence of suchnon-polar solvents is known to produce polyenes with high 1,4-contentsfrom 1,3-dienes. Inert hydrocarbon solvents useful in practicing thisinvention include but are not limited to inert liquid alkanes,cycloalkanes and aromatic solvents and mixtures thereof. Exemplaryalkanes and cycloalkanes include those containing five to 10 carbonatoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane,methylcycloheptane, octane, decane and the like and mixtures thereof.Exemplary aryl solvents include those containing six to ten carbonatoms, such as toluene, ethylbenzene, p-xylene, m-xylene, o-xylene,n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like andmixtures thereof.

Polar modifiers can be added to the polymerization reaction to alter themicrostructure of the resulting polymer, i.e., increase the proportionof 1,2 (vinyl) microstructure or to promote functionalization orrandomization. Examples of polar modifiers include, but are not limitedto: diethyl ether, dibutyl ether, tetrahydrofuran (THF),2-methyltetrahydrofuran, methyl tert-butyl ether (MTBE),diazabicyclo[2.2.2]octane (DABCO), triethylamine, tri-n-butylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), and 1,2-dimethoxyethane(glyme). The amount of the polar modifier added depends on the vinylcontent desired, the nature of the monomer, the temperature of thepolymerization, and the identity of the polar modifier.

The polymers can be optionally hydrogenated. Protecting groups whenpresent on the functionalizing agents and/or initiators can also beoptionally removed, prior to or following hydrogenation. Removal of theprotecting group(s) (deprotection) produces polymers with at least onefunctional group (e.g. oxygen, sulfur and/or nitrogen) per polymer chainon the ends of the polymer arms. The functional groups can thenparticipate in various copolymerization reactions by reaction of thefunctional groups on the ends of the polymer arms with selecteddifunctional or polyfunctional comonomers.

Deprotection can be performed either prior to or after the optionalhydrogenation of the residual unsaturation. For example, to removetert-alkyl-protected groups, the protected polymer can be mixed withAmberlyst® 15 ion exchange resin and heated at an elevated temperature,for example 150° C., until deprotection is complete.Tert-alkyl-protected groups can also be removed by reaction of thepolymer with para-toluensulfonic acid, trifluoroacetic acid, ortrimethylsilyliodide. Additional methods of deprotection of thetert-alkyl protecting groups can be found in T. W. Greene and P. G. M.Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, NewYork, 1991, page 41.

Tert-butyldimethylsilyl protecting groups can be removed by treatment ofthe copolymer with acid, such as hydrochloric acid, acetic acid,para-toluensulfonic acid, or Dowex® 50W-X8. Alternatively, a source offluoride ions, for instance tetra-n-butylammonium fluoride, potassiumfluoride and 18-crown-6, or pyridine-hydrofluoric acid complex, can beemployed for deprotection of the tert-butyldimethylsilyl protectinggroups. Additional methods of deprotection of thetert-butyldimethylsilyl protecting groups can be found in T. W. Greeneand P. G. M. Wuts, Protective Groups in Organic Synthesis, SecondEdition, Wiley, New York, 1991, pages 80-83.

The progress of the deprotection reactions can be monitored byconventional analytical techniques, such as Thin Layer Chromatography(TLC), Nuclear Magnetic Resonance (NMR) spectroscopy, or InfraRed (IR)spectroscopy.

Hydrogenation techniques are described in U.S. Pat. Nos. 4,970,254,5,166,277, 5,393,843 and 5,496,898, the entire disclosure of each ofwhich is incorporated by reference. The hydrogenation of the polymer isconducted in situ, or in a suitable solvent, such as hexane, cyclohexaneor heptane. This solution is contacted with hydrogen gas in the presenceof a catalyst, such as a nickel catalyst. The hydrogenation is typicallyperformed at temperatures from 25° C. to 150° C., with a archetypalhydrogen pressure of 15 psig to 1000 psig. The progress of thishydrogenation can be monitored by InfraRed (IR) spectroscopy or NuclearMagnetic Resonance (NMR) spectroscopy. The hydrogenation reaction can beconducted until at least 90% of the aliphatic unsaturation has beensaturated. The hydrogenated polymer is then recovered by conventionalprocedures, such as removal of the catalyst with aqueous acid wash,followed by solvent removal or precipitation of the polymer.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 Preparation of Dimethylaminopropylpolystyrene

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (90ml.). S-butyllithium, 0.149 grams (2.3 mmole, 1.45 M in cyclohexane, 1.6mL) was then added via syringe. Purified styrene monomer (9.30 grams,89.3 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The living poly(styryl)lithiumwas then transferred into an ampoule and the known amount of residualsolution was terminated with degassed methanol from the last ampoule toobtain a base polymer sample. A second 250 ml. glass reactor wasequipped with three break-seal reagent ampoules, a sampling portattached with a Teflon® stopcock, an inlet tube fitted with a septumcap, and a magnetic stir bar. This reactor was flame sealed to a highvacuum line, and evacuated at 120° C. for 8 hours. The flask wasrefilled with dry argon, and allowed to cool to room temperature.Lithium chloride (0.133 grams, 3.14 mmols) was added to the secondreactor and dried by heating at 150° C. for an hour under vacuum. Theflask was then allowed to cool to room temperature. Thepoly(styryl)lithium (90 ml, 2.09 mmols) was transferred to one of theampoules. The second ampoule was charged with a benzene solution of3-(N,N-dimethylamino)-1-chloropropane (0.383 grams, 3.14 mmols). Thepoly(styryl)lithium solution and the solution of3-(,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:M _(n)=4.0×10³ g/mole M _(w) /M _(n)=1.07

End-group titration of the functionalized polymer indicated that thefunctionality was 0.92.

COMPARATIVE EXAMPLE Preparation of Dimethylaminopropylpolystyrene, NoAdditive

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (75ml.). S-Butyllithium, 0.251 grams (3.9 mmole, 1.45 M in cyclohexane, 2.7mL) was then added via syringe. Purified styrene monomer (8.50 grams,81.6 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The living poly(styryl)lithiumwas then transferred into an ampoule and the known amount of residualsolution was terminated with degassed methanol from the last ampoule toobtain a base polymer sample. A second 250 ml. glass reactor wasequipped with three break-seal reagent ampoules, a sampling portattached with a Teflon® stopcock, an inlet tube fitted with a septumcap, and a magnetic stir bar. This reactor was flame sealed to a highvacuum line, and evacuated at 120° C. for 8 hours. The flask wasrefilled with dry argon, and allowed to cool to room temperature. Thepoly(styryl)lithium (75 ml, 3.7 mmols) was transferred to one of theampoules. The second ampoule was charged with a benzene solution of3-(N,N-dimethylamino)-1-chloropropane (0.677 grams, 5.55 mmols). Thepoly(styryl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:

 M _(n)=2.2×10³ g/moleM _(w) /M _(n)=1.05

End-group titration of the functionalized polymer indicated that thefunctionality was 0.65.

EXAMPLE 2 Preparation of Dimethylaminopropylpolyisoprene

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (90ml.). S-Butyllithium, 0.149 grams (2.3 mmole, 1.45 M in cyclohexane, 1.6mL) was then added via syringe. Purified isoprene monomer (9.00 grams,132.1 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was then transferred into an ampoule and theknown amount of residual solution was terminated with degassed methanolfrom the last ampoule to obtain a base polymer sample. A second 250 ml.glass reactor was equipped with three break-seal reagent ampoules, asampling port attached with a Teflon® stopcock, an inlet tube fittedwith a septum cap, and a magnetic stir bar. This reactor was flamesealed to a high vacuum line, and evacuated at 120° C. for 8 hours. Theflask was refilled with dry argon, and allowed to cool to roomtemperature. Lithium chloride (0.133 grams, 3.14 mmols) was added to thesecond reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium (90 ml, 2.09 mmols) was transferred to one of theampoules. The second ampoule was charged with a cyclohexane solution of3-(N,N-dimethylamino)-1-chloropropane (0.383 grams, 3.14 mmols). Thepoly(isoprenyl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was air dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:M _(n)=3.9×10³ g/moleM _(w) /M _(n)=1.08

End-group titration of the functionalized polymer indicated that thefunctionality was 1.02.

COMPARATIVE EXAMPLE Preparation of Dimethylaminopropylpolyisoprene, NoAdditive

A 250 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (75ml.). S-Butyllithium, 0.251 grams (3.9 mmole, 1.45 M in cyclohexane, 2.7mL) was then added via syringe. Purified isoprene monomer (7.10 grams,104 mmoles) was added from a break-seal ampoule. The reaction mixturewas kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was then transferred into an ampoule and theknown amount of residual solution was terminated with degassed methanolfrom the last ampoule to obtain a base polymer sample. A second 250 ml.glass reactor was equipped with three break-seal reagent ampoules, asampling port attached with a Teflon® stopcock, an inlet tube fittedwith a septum cap, and a magnetic stir bar. This reactor was flamesealed to a high vacuum line, and evacuated at 120° C. for 8 hours. Theflask was refilled with dry argon, and allowed to cool to roomtemperature. The poly(isoprenyl)lithium (75 ml, 3.7 mmols) wastransferred to one of the ampoules. The second ampoule was charged witha cyclohexane solution of 3-(N,N-dimethylamino)-1-chloropropane (0.677grams, 5.55 mmols). The poly(isoprenyl)lithium solution and the solutionof 3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was air dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:M _(n)=1.8×10³ g/moleM _(w) /M _(n)=1.08

End-group titration of the functionalized polymer indicated that thefunctionality was 0.81.

EXAMPLE 3 Preparation ofAlpha-Hydroxy-Omega-Dimethylaminopropylpolystyrene

A 500 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified benzene (250ml.). 3-(1,1-Dimethylethoxy)-1-propyllithium, chain extended with twoequivalents of isoprene, 0.90 grams (3.5 mmole, 0.52 M in cyclohexane,6.7 mL) was then added via syringe. Purified styrene monomer (28.15grams, 89.3 mmoles) was added from a break-seal ampoule. The reactionmixture was kept for 6 hours at room temperature. The livingpoly(styryl)lithium was divided equally into three calibrated ampoulesfor reaction with the alkyl chlorides. The residual solution wasterminated with degassed methanol from the last ampoule to obtain a basepolymer sample. A second 250 ml. glass reactor was equipped with threebreak-seal reagent ampoules, a sampling port attached with a Teflon®stopcock, an inlet tube fitted with a septum cap, and a magnetic stirbar. This reactor was flame sealed to a high vacuum line, and evacuatedat 120° C. for 8 hours. The flask was refilled with dry argon, andallowed to cool to room temperature. Lithium chloride (0.041 grams, 0.97mmols) was added to the second reactor and dried by heating at 150° C.for an hour under vacuum. The flask was then allowed to cool to roomtemperature. The poly(styryl)lithium (80 ml, 0.97 mmols) was transferredto one of the ampoules. The second ampoule was charged with a benzenesolution of 3-(N,N-dimethylamino)-1-chloropropane (0.18 grams, 1.46mmoles). The poly(styryl)lithium solution and the solution of3-(N,N-dimethylamino)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:M _(n)=8.3×10³ g/moleM _(w) /M _(n)=1.22

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃) and a dimethylaminogroup from the electrophile (δ=2.20 ppm for the —N(CH₃)₂).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylaminopropylpolystyrene polymer was isolatedand characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.98. Examination of the ¹H NMR of thisheterotelechelic polymer indicated a dimethylamino (δ=2.20 ppm for the—N(CH₃)₂) functionality of 0.91.

EXAMPLE 4 Preparation ofAlpha-Hydroxy-Omega-Dimethylethylthiopropylpolystyrene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.041 grams, 0.97 mmols) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(styryl)lithium, prepared in Example 3 above, (80 ml, 0.97 mmols)was transferred to one of the ampoules. The second ampoule was chargedwith a benzene solution of 3-(dimethylethylthio)-1-chloropropane (0.24grams, 1.46 mmoles). The poly(styryl)lithium solution and the solutionof 3-(dimethylethylthio)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. Theresultant functionalized polymer solution was precipitated into a largeamount of methanol and the recovered polymer was air dried for 24 hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:M _(n)=8.3×10³ g/moleM _(w) /M _(n)=1.22

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃), and the t-butyl groupfrom the electrophile (δ=1.41 ppm for the —SC(CH₃)₃).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylethylthiopropylpolystyrene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.95.

EXAMPLE 5 Preparation of Alpha-Hydroxy-Omega-Aminopropylpolystyrene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.041 grams, 0.97 mmols) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(styryl)lithium, prepared in Example 3 above, (80 ml, 0.97 mmols)was transferred to one of the ampoules. The second ampoule was chargedwith a benzene solution ofN-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane (0.388grams, 1.46 mmoles). The poly(styryl)lithium solution and the solutionof N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane wereadded sequentially to the reactor by breaking the correspondingbreakseals. The reaction mixture was kept at room temperature for 6hours with stirring. A small sample was withdrawn with a syringe throughthe sample port for ¹H NMR analysis. Degassed methanol was then addedfrom the remaining break-seal ampoule. The resultant functionalizedpolymer solution was precipitated into a large amount of methanol. Thesilyl protecting group was removed by washing the polymer cement fivetimes with methanol and the recovered polymer was air dried for 24hours.

The resultant base polystyrene polymer was characterized by SEC(polystyrene standards), and had the following properties:M _(n)=8.3×10³ g/moleM _(w) /M _(n)=1.22

Examination of the ¹H NMR of this heterotelechelic polymer (prior todeprotection) indicated the presence of the t-butyl group from theinitiator (δ=1.17 ppm for the —OC(CH₃)₃) and indicated a siliconprotecting group (δ=0.08 ppm for the —Si(CH₃)₂—)functionality of 0.99.

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultant alpha-hydroxyl-omega-aminopropylpolystyrenepolymer was isolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 1.02.

EXAMPLE 6 Preparation ofAlpha-Hydroxy-Omega-Dimethylaminopropylpolyisoprene

A 500 ml. glass reactor was equipped with two break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. The reactor was charged with purified cyclohexane (300ml.). 3-(1,1-Dimethylethoxy)-1-propyllithium, chain extended with twoequivalents of isoprene, 1.81 grams (7.0 mmole, 0.52 M in cyclohexane,13.5 mL) was then added via syringe. Purified isoprene monomer (23.15grams, 340 mmoles) was added from a break-seal ampoule. The reactionmixture was kept for 6 hours at room temperature. The livingpoly(isoprenyl)lithium was divided equally into three calibratedampoules for reaction with the alkyl chlorides. The residual solutionwas terminated with degassed methanol from the last ampoule to obtain abase polymer sample. A second 250 ml. glass reactor was equipped withthree break-seal reagent ampoules, a sampling port attached with aTeflon® stopcock, an inlet tube fitted with a septum cap, and a magneticstir bar. This reactor was flame sealed to a high vacuum line, andevacuated at 120° C. for 8 hours. The flask was refilled with dry argon,and allowed to cool to room temperature. Lithium chloride (0.128 grams,3.03 mmoles) was added to the second reactor and dried by heating at150° C. for an hour under vacuum. The flask was then allowed to cool toroom temperature. The poly(isoprenyl)lithium (95 ml, 2.02 mmoles) wastransferred to one of the ampoules. The second ampoule was charged witha cyclohexane solution of 3-(N,N-dimethylamino)-1-chloropropane (0.37grams, 3.03 mmoles). The poly(isoprenyl)lithium solution and thesolution of 3-(N,N-dimethylamino)-1-chloropropane were addedsequentially to the reactor by breaking the corresponding breakseals.The reaction mixture was kept at room temperature for 6 hours withstirring before quenched by addition of degassed methanol from the lastbreak-seal ampoule. BHT (2,6-di-t-butyl-4-methylphenol, 0.1 wt %) wasadded to the polymer solution as an antioxidant. The resultantfunctionalized polymer solution was precipitated into a large amount ofmethanol and the recovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:M _(n)=3.2×10³ g/moleM _(w) /M _(n)=1.06

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃) and a dimethylaminogroup from the electrophile (δ=2.20 ppm for the —N(CH₃)₂).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylaminopropylpolyisoprene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.92. Examination of the ¹H NMR of thisheterotelechelic polymer indicated a dimethylamino (δ=2.20 ppm for the—N(CH₃)₂) functionality of 0.90.

EXAMPLE 7 Preparation ofAlpha-Hydroxy-Omega-Dimethylethylthiopropylpolyisoprene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.128 grams, 3.03 mmoles) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium, prepared in Example 6 above, (95 ml, 2.02mmoles) was transferred to one of the ampoules. The second ampoule wascharged with a cyclohexane solution of3-(dimethylethylthio)-1-chloropropane (0.50 grams, 3.03 mmoles). Thepoly(isoprenyl)lithium solution and the solution of3-(dimethylethylthio)-1-chloropropane were added sequentially to thereactor by breaking the corresponding breakseals. The reaction mixturewas kept at room temperature for 6 hours with stirring before quenchedby addition of degassed methanol from the last break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol and therecovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:M _(n)=3.2×10³ g/moleM _(w) /M _(n)=1.06

Examination of the ¹H NMR indicated the presence of the t-butyl groupfrom the initiator (δ=1.17 ppm for the —OC(CH₃)₃), and the t-butyl groupfrom the electrophile (δ=1.41 ppm for the —SC(CH₃)₃).

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultantalpha-hydroxyl-omega-dimethylethylthiopropylpolyisoprene polymer wasisolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.96.

EXAMPLE 8 Preparation of Alpha-Hydroxy-Omega-Aminopropylpolyisoprene

A 250 ml. glass reactor was equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor wasflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask was refilled with dry argon, and allowed to cool toroom temperature. Lithium chloride (0.128 grams, 3.03 mmoles) was addedto the reactor and dried by heating at 150° C. for an hour under vacuum.The flask was then allowed to cool to room temperature. Thepoly(isoprenyl)lithium, prepared in Example 6 above, (95 ml, 2.02mmoles) was transferred to one of the ampoules. The second ampoule wascharged with a cyclohexane solution ofN-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentane (0.805grams, 3.03 mmoles). The poly(isoprenyl)lithium solution and thesolution of N-3-chloropropyl-2,2,5,5-tetramethyl-2,5-disila-1-azapentanewere added sequentially to the reactor by breaking the correspondingbreakseals. The reaction mixture was kept at room temperature for 6hours with stirring. A small sample was withdrawn with a syringe throughthe sample port for ¹H NMR analysis. Degassed methanol was then addedfrom the remaining break-seal ampoule. BHT(2,6-di-t-butyl-4-methylphenol, 0.1 wt %) was added to the polymersolution as an antioxidant. The resultant functionalized polymersolution was precipitated into a large amount of methanol. The silylprotecting group was removed by washing the polymer cement five timeswith methanol and the recovered polymer was vacuum dried for 24 hours.

The resultant base polyisoprene polymer was characterized by SEC(polyisoprene standards), and had the following properties:M _(n)=3.2×10³ g/moleM _(w) /M _(n)=1.06

Examination of the ¹H NMR of this heterotelechelic polymer (prior todeprotection) indicated the presence of the t-butyl group from theinitiator (δ=1.17 ppm for the —OC(CH₃)₃) and indicated a siliconprotecting group (δ=0.08 ppm for the —Si(CH₃)₂—) functionality of 1.02.

Removal of tertiary butyl group protecting group was effected byreaction of the alpha, omega heterotelechelic functionalized polymer,prepared above, with Amberlyst-15® in cyclohexane for 6 hours underreflux. The resultant alpha-hydroxyl-omega-aminopropylpolyisoprenepolymer was isolated and characterized.

End-group titration of the functionalized polymer indicated that thefunctionality was 0.91.

EXAMPLE 9 Preparation of Telechelic Alpha, Omega-Dihydroxy-Polyisoprene

A 1000 ml. glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and is allowed to cool toroom temperature. Lithium chloride (0.64 grams, 15 mmoles) is added tothe reactor and dried by heating at 150° C. for an hour under vacuum.The flask is then allowed to cool to room temperature. The reactor ischarged with purified cyclohexane (500 ml.). S-Butyllithium, 0.64 grams(10 mmoles, 1.45 M in cyclohexane, 6.9 mL) is then added via syringe.1,3-Diisopropenylbenzene, 7.91 grams (5 mmoles) is added from a breakseal ampoule. The reactor is stirred for sixty minutes at roomtemperature, to form the dilithium initiator. Purified isoprene monomer(100 grams, 1.468 moles) is added from a break-seal ampoule. Thereaction mixture is kept for six hours at room temperature. A solutionof 3.13 grams (15 mmoles) 3-(t-butyldimetylsilyloxy)-1-chloropropane isadded to the reactor by breaking the corresponding breakseal. Thereaction mixture is kept at room temperature for six hours with stirringbefore quenched by addition of degassed methanol from the lastbreak-seal ampoule. BHT (2,6-di-t-butyl-4-methylphenol, 0.1 wt %) isadded to the polymer solution as an antioxidant. The resultanthomotelechelic functionalized polymer solution is precipitated into alarge amount of methanol and the recovered polymer was vacuum dried for24 hours.

The resultant base polyisoprene polymer is characterized by SEC(polyisoprene standards), and has the following properties:M _(n)=1.05×10⁴ g/moleM _(w) /M _(n)=1.06

Examination of the ¹H NMR indicates the presence of thet-butyldimethylsilyl group from the electrophile (δ=0.09 ppm for the—Si(CH₃)₃).

Removal of t-butyldimethylsilyl group protecting group is effected byreaction of the alpha, omega homotelechelic functionalized polymer,prepared above, with 1 N HCl in tetrahydrofuran for 6 hours underreflux. The resultant alpha, omega-dihydroxylpolyisoprene polymer isisolated and characterized.

End-group titration of the deprotected, functionalized polymer indicatesthat the functionality is 1.94.

The foregoing examples are illustrative of the present invention and arenot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

1. A process for improving the efficiency of the coupling reactionbetween polymer anions and electrophiles, the process comprisingreacting one or more living polymer anions with one or moreelectrophiles in the presence of an additive capable of increasing thefunctionalization reaction and selected from the group consisting ofalkali halides, alkali alkoxides and mixtures thereof.
 2. The process ofclaim 1, wherein said one or more alkali halides are selected from thegroup consisting lithium chloride, lithium bromide, lithium iodide,sodium iodide, potassium chloride, and mixtures thereof.
 3. The processof claim 1, wherein said one or more electrophiles comprises one or morecompounds selected from the group consisting of

and mixtures thereof, wherein X is halogen selected from the groupconsisting of chloride, bromide and iodide; Z is a branched or straightchain hydrocarbon connecting group which contains 1-25 carbon atoms,optionally containing aryl or substituted aryl groups; T is selectedfrom the group consisting of oxygen, sulfur, and nitrogen groups andmixtures thereof, (A˜R⁷R⁸R⁹)m is a protecting group in which A is anelement selected from Group IVa of the Periodic Table of the Elements,and R⁷, R⁸, and R⁹ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl; m is 1 when T is oxygen orsulfur, and 2 when T is nitrogen; and l is an integer from 1 to
 7. 4.The process of claim 1, wherein said one or more electrophiles comprisesone or more compounds selected from the group consisting of

and mixtures thereof, wherein: X is a halogen selected from chloride,bromide and iodide; Z is a branched or straight chain hydrocarbonconnecting group which contains 1-25 carbon atoms, optionallysubstituted with aryl or substituted aryl; T is selected from the groupconsisting of oxygen, sulfur, nitrogen, and mixtures thereof; (A-R₁R₂R₃)is a protecting group, in which A is an element selected from Group IVaof the Periodic Table of the Elements and R₁, R₂, and R₃ are eachindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, and substitutedcycloalkyl; R, R₄, and R₅ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl; h is 0 when T is oxygen orsulfur, and 1 when T is nitrogen; l is an integer from 1 to 7; m is 1when T is oxygen or sulfur, and 2 when T is nitrogen; and n is 2 or 3.5. The process of claim 1, wherein said one or more electrophilescomprises one or more compounds of the formulaX-Z-Si—[T-(A-R₁-R₂-R₃)_(m)]_(n)  (VI) wherein: X is halogen selectedfrom the group consisting of chloride, bromide and iodide; Z is abranched or straight chain hydrocarbon connecting group which contains1-25 carbon atoms, optionally substituted with aryl or substituted aryl;T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof; A is an element selected from Group IVa ofthe Periodic Table of the Elements; R₁, R₂, and R₃ are eachindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, and substitutedcycloalkyl; m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;and n is 2 or
 3. 6. The process of claim 1, wherein said one or moreelectrophiles comprises one or more compounds of the formula

wherein: Z′ is a halogen atom; R₁₃ is selected from the group consistingof organic groups containing from 1 to about 12 carbon atoms and abridging bond; each R₁₄ is independently selected from the groupconsisting of hydrogen, organic groups containing from 1 to about 12carbon atoms and a bridging bond; each R₁₅ is independently selectedfrom the group consisting of hydrogen, organic groups containing from 1to about 12 carbon atoms; a is an integer from 4 to about 16 ; and b isan integer from 0 to about
 12. 7. The process of claim 1, furthercomprising prior to said functionalizing step the step of anionicallypolymerizing one or more anionically polymerizable monomers selectedfrom the group consisting of one or more conjugated diene, one or morealkenylsubstituted aromatic compound, and mixtures of one or moreconjugated dienes with one or more alkenylsubstituted aromatic compoundsin a hydrocarbon or mixed hydrocarbon-polar solvent medium at atemperature of 10° C. to 150° C. with one or more functionalized ornon-functionalized initiators to form a composition comprising one ormore living polymer anions.
 8. The process of claim 7, comprisinganionically polymerizing said one or more anionically polymerizablemonomers with one or more non-functionalized initiators.
 9. The processof claim 8, wherein said one or more non-functionalized initiatorscomprises one or more alkyllithium initiators of the formula R′-Li,wherein R′ is an aliphatic, cycloaliphatic, or arylsubstituted aliphaticradical.
 10. The process of claim 9, wherein said one or morealkyllithium initiators are selected from the group consisting of methyllithium, ethyllithium, n-propyllithium, 2-propyllithium, n-butyllithium,s-butyllithium, t-butyl lithium, n-hexyllithium, 2-ethylhexyllithium,and mixtures thereof.
 11. The process of claim 10, wherein said one ormore alkyllithium initiators comprises butyllithium.
 12. The process ofclaim 8, wherein said one or more non-functionalized initiatorscomprises one or more dilithium initiators.
 13. The process of claim 7,comprising anionically polymerizing said one or more anionicallypolymerizable monomers with one or more functionalized initiators. 14.The process of claim 13, wherein said one or more functionalizedinitiators comprises one or more initiators selected from the groupconsisting of:

and mixtures thereof, wherein: M is an alkali metal selected from thegroup consisting of lithium, sodium and potassium; Q is an unsaturatedhydrocarbyl group derived by incorporation of one or more conjugateddiene hydrocarbons, one or more alkenylsubstituted aromatic compounds,or mixtures of one or more dienes with one or more alkenylsubstitutedaromatic compounds into the M-Z linkage; n is an integer from 0 to 5; Zis a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl; T is selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof; (A-R⁷R⁸R⁹)_(m) is aprotecting group in which A is an element selected from Group IVa of thePeriodic Table of the Elements, and R⁷, R⁸, and R⁹ are eachindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, and substitutedcycloalkyl; l is an integer from 1 to 7; and m is 1 when T is oxygen orsulfur, and 2 when T is nitrogen.
 15. The process of claim 13, whereinsaid one or more functionalized initiators comprises one or moreinitiators selected from the group consisting of:

and mixtures thereof, wherein: M is an alkali metal selected from thegroup consisting of lithium, sodium and potassium; Q is an unsaturatedhydrocarbyl group derived by incorporation of one or more conjugateddiene hydrocarbons, one or more alkenylsubstituted aromatic compounds,or mixtures of one or more dienes with one or more alkenylsubstitutedaromatic compounds into the M-Z linkage; n is an integer from 0 to 5;R¹⁰ chiral or achiral and is selected from the group consisting ofsaturated and unsaturated, linear and branched, optionally silyl-,amino-, or oxy-substituted, C3-C16 alkyl; and saturated and unsaturated,linear and branched, C3-C16 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl; R¹¹ is chiral or achiral and isselected from the group consisting of saturated and unsaturated, linearand branched, optionally silyl-, amino-, or oxy-substituted, C1-C16alkyl; saturated and unsaturated, optionally silyl-, amino-, oroxy-substituted, C3-C16 cycloalkyl; saturated and unsaturated, linearand branched, substituted C1-C16 alkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; and saturated andunsaturated substituted C3-C16 cycloalkyl containing saturated orunsaturated lower alkyl, aryl, or substituted aryl; and R¹² is ahydrocarbon connecting group or tether selected from the groupconsisting of saturated and unsaturated, linear and branched C1-C25alkyl; saturated and unsaturated C3-C25 cycloalkyl; saturated andunsaturated substituted C1-C25 alkyl containing saturated or unsaturatedlower alkyl, aryl, or substituted aryl; and saturated and unsaturatedsubstituted C3-C25 cycloalkyl containing saturated or unsaturated loweralkyl, aryl, or substituted aryl, with the proviso that the nitrogenatom and the alkali metal are separated by three or more carbon atoms.16. The process of claim 1, wherein said one or more additives ispresent in an amount sufficient to improve the efficiency of thefunctionalization reaction at least about 25% as compared to the samereaction without the additive.
 17. The process of claim 16, wherein saidone or more additives is present in an amount sufficient to improve theefficiency of the functionalization reaction at least about 40% ascompared to the same reaction without the additive.
 18. The process ofclaim 1, wherein said one or more additives is present in an amountranging from about 0.01 to about 5 equivalents, based on the amount ofelectrophile.
 19. The process of claim 18, wherein said one or moreadditives is present in an amount ranging from about 0.5 to about 1.5equivalents, based on the amount of electrophile.
 20. The process ofclaim 1, wherein said electrophile comprises one or more electrophilesfor coupling two or more living polymers to form a multi-branched orstar polymer.
 21. The process of claim 1, wherein said electrophilecomprises one or more alkyl halide electrophiles.
 22. The process ofclaim 1, wherein said reacting step is conducted in hydrocarbon solvent.23. The process of claim 1, wherein said reacting step is conducted atroom temperature.
 24. The process of claim 7, comprising conducting saidanionic polymerization in the presence of said one or more additives.25. The process of claim 24, comprising adding said one or moreadditives as a separate component prior to said polymerization step. 26.The process of claim 24, comprising adding said one or more additives asa component of a composition comprising said one or more initiators. 27.The process of claim 24, comprising adding said one or more additives asa separate component during said polymerization step.
 28. The process ofclaim 7, further comprising adding said one or more additives to saidliving polymer anion composition after said polymerization step.
 29. Theprocess of claim 28, comprising adding said one or more additives as aseparate component to said living polymer anion composition.
 30. Theprocess of claim 28, comprising adding said one or more additives as acomponent of an electrophile composition to said living polymer anioncomposition.
 31. A process for improving the efficiency of the couplingreaction between polymer anions and electrophiles, the processcomprising: anionically polymerizing one or more anionicallypolymerizable monomers in a hydrocarbon or mixed hydrocarbon-polarsolvent medium at a temperature of 10° C. to 150° C. with one or morefunctionalized or non-functionalized initiators to form a compositioncomprising one or more living polymer anions; and adding one or moreadditives capable of increasing the functionalization of living polymeranions with one or more electrophiles to said living polymer anioncomposition, wherein the additive is selected from the group consistingof alkali halides, alkali alkoxides and mixture thereof; and adding oneor more electrophiles to said living polymer composition tofunctionalize said living polymer anion composition in the presence ofsaid one or more additives.
 32. The process of claim 31, wherein saidinitiator comprises an alkyllithium and said additive comprises analkali halide.
 33. The process of claim 32, wherein said alkyllithium isbutyllithium and said alkali halide is lithium chloride.
 34. The processof claim 31, wherein the steps of adding said one or more additives andadding said one or more electrophiles are conducted sequentially.